Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 2. Original paint layer samples

The darkening of the original yellow areas painted with the chrome yellow pigment (PbCrO(4), PbCrO(4)·xPbSO(4), or PbCrO(4)·xPbO) is a phenomenon widely observed on several paintings by Vincent van Gogh, such as the famous different versions of Sunflowers. During our previous investigations on artificially aged model samples of lead chromate, we established for the first time that darkening of chrome yellow is caused by reduction of PbCrO(4) to Cr(2)O(3)·2H(2)O (viridian green), likely accompanied by the presence of another Cr(III) compound, such as either Cr(2)(SO(4))(3)·H(2)O or (CH(3)CO(2))(7)Cr(3)(OH)(2) [chromium(III) acetate hydroxide]. In the second part of this work, in order to demonstrate that this reduction phenomenon effectively takes place in real paintings, we study original paint samples from two paintings of V. van Gogh. As with the model samples, in view of the thin superficial alteration layers that are present, high lateral resolution spectroscopic methods that make use of synchrotron radiation (SR), such as microscopic X-ray absorption near edge (μ-XANES) and X-ray fluorescence spectrometry (μ-XRF) were employed. Additionally, μ-Raman and mid-FTIR analyses were carried out to completely characterize the samples. On both paint microsamples, the local presence of reduced Cr was demonstrated by means of μ-XANES point measurements. The presence of Cr(III) was revealed in specific areas, in some cases correlated to the presence of Ba(sulfate) and/or to that of aluminum silicate compounds.     

Advanced methods for natural product drug discovery in the field of nutraceuticals

Advances in analytical methods and bioassay development have helped to push forward the research in natural products. In plant extracts and nutraceuticals, bioactive compounds are part of a complex mixture. The development of high-resolution methods related to HPLC for both chemical and biological profiling has significantly increased the efficiency of classical bioactivity-guided fractionation procedures. Furthermore, the level of sensitivity obtained by these methods give the possibility to work with few micrograms of compound. This represents a key advantage for rapid localisation of the biological activity and subsequent identification of the compounds of interest. The same methods are also used to study the extracts from a metabolomic view point. The possibility to study them as a whole can highlight synergetic effects, which are likely to occur in plant extracts and nutraceuticals. In this paper, the main trends are summarised and the developments made in our laboratory on profiling crude extracts with UHPLC-TOF-MS, natural product identification at the microgram level using microflow NMR and integration of these methods with biological evaluation are highlighted.     

Plants as a source of therapeutic and health products

The research unit of Pharmacognosy is mostly working on the biological activity and safety of natural products, as well as herbal dietary supplements. One of the focuses relies on finding new cancer chemopreventive compounds by means of a battery of short-term in vitro bioassays developed to monitor inhibition of tumorigenesis at various stages. Neglected diseases are a major problem in developing countries. Therefore, the search for new or improved treatments is also needed and consists of another area of research of the unit. For both projects, in-depth mechanistic studies, as well as in vitro and in vivo absorption and metabolization experiments are performed. Problems related to undeclared, unauthorized or toxic botanicals in herbal dietary supplements are of growing importance as they generally have not gone through a rigorous drug testing process as for therapeutic phytochemicals. For this, a generic method was developed for the multi-targeted screening of biomarkers which aims at characterizing plant species in these supplements.     

Development of a laboratory scale clean-in-place system to test the effectiveness of "natural" antimicrobials against dairy biofilms

A laboratory scale system, partially reproducing dairy plant conditions, was developed to quantify the effectiveness of chlorine and alternative sanitizers in reducing the number of viable bacteria attached to stainless steel surfaces. Stainless steel tubes fouled in a continuous flow reactor were exposed to a standard clean-in-place regime (water rinse, 1% sodium hydroxide at 70 degrees C for 10 min, water rinse, 0.8% nitric acid at 70 degrees C for 10 min, water rinse) followed by exposure to either chlorine (200 ppm) or combinations of nisin (500 ppm), lauricidin (100 ppm), and the lactoperoxidase system (LPS) (200 ppm) for 10 min or 2, 4, 8, 18, or 24 h. There was significant variation in the effectiveness of the alkaline-acid wash steps in reducing cell numbers (log reduction between 0 and 2). Following a 10-min treatment, none of the sanitizers significantly reduced the number of attached cells. Two hours of exposure to chlorine, nisin + the LPS, or lauricidin + the LPS achieved 2.8, 2.2, and 1.6 log reductions, respectively. Exposure times > 2 h did not further decrease the number of viable bacteria attached to the stainless steel. The effectiveness of combinations of nisin, lauricidin, and the LPS was similar to that of chlorine (P > 0.05), and these sanitizers could be used to decontaminate the surfaces of small-volume or critical hard-to-clean milk processing equipment.     

The effect of the acid/dithionite/peroxide treatments on reactively dyed cotton and indigo dyed denim and the implications for waste cellulosic recycling

Abstract

Previous studies have established that the application of crosslinking dyes and easy care finishes to cotton can significantly reduce the dissolution of waste cotton in swelling solvents and limit potential recycling of cellulosic materials through Lyocell fibre regeneration process. In this study, a sequential hydrolysis/reduction/oxidative treatment was investigated as a potential method to completely strip all types of reactive dye chromophores from cotton. It was established that the treatment could completely strip off colours from the reactively dyed fabrics and post-consumer denim jeans fabric resulting in a white, NMMO-dissolvable cellulosic material, which could be used as a feedstock for Lyocell fibre regeneration. The white cellulose had an acceptable degree of polymerisation and the regenerated fibres had structural and mechanical properties similar to those of fibres regenerated from conventional wood pulp. Blending conventional wood pulp and recycled cotton pulp allowed manufacturing of regenerated Lyocell-type fibres with acceptable properties.     

Effect of duration of the Montanera diet on the hydrocarbon fraction of intramuscular lipids from Iberian dry‐cured ham; characterization by gas chromatography

The characterization and differentiation of Iberian hams was studied as a function of the diet received by animals during the fattening period using a method based on hydrocarbon analysis. Thirty‐one hams were divided into three groups according to fattening diet (1, ‘Concentrate Feed’, fed on an intensive system with concentrates; 2, ‘Short Montanera’, fed on an extensive system with acorns and pasture for 50 days; and 3, ‘Long Montanera’, fed on an extensive system for 75 days). Saturated hydrocarbons in the n‐C₁₄ to n‐C₃₂ range and a large number of branched hydrocarbons were identified in the intramuscular fat of the three groups studied. The diet of the pigs during the fattening period did not affect the n‐alkane and n‐alkene content. The analysis of branched hydrocarbons revealed some significant differences relative to the type of diet. The ‘Concentrate Feed’ group had different concentrations of 2‐butyl‐1,1,3‐trimethylcyclohexane (P < 0.01), 3‐octadecene (P < 0.001), branched hydrocarbon 4 (P < 0.01) and neophytadiene (P < 0.001) than the ‘Montanera’ group. Copyright © 2006 Society of Chemical Industry     

Microstructure and physico-chemical evaluation of nano-emulsion-based antimicrobial peptides embedded in bioactive packaging films

Customized application of antimicrobial peptide (AMP) ‘nisin’ directly into food (neither in active packaging nor encapsulated form) is expensive and associated with loss of activity due to deactivation in complex food systems. The purpose of the present study was to fusion the two concepts for improved bioavailability i.e. AMP nanoencapsulation and biopolymer immobilizing to formulate the next generation biodegradable films embedded with either active agent, nano-encapsulated active agent or both of them. Nanoliposomes were prepared using soy-lecithin by microfluidizer at 2000 bar with 5 cycles to generate an average size of 151 ± 4 nm with 50 ± 3% encapsulation efficiency. For active films, nisin had demonstrated no negative impact on transparency, thickness and water sorption behavior obtained by GAB model (25 °C, 0–0.95 a_w). For nano-active films, the results clearly illustrated that different physico-chemical properties including barrier (oxygen and water vapor permeability), color and transparency (200–900 nm) remained comparable to native hydroxypropyl methylcellulose (HPMC) films and were significantly improved than using lecithin directly without nano-scale restructuring. The microstructure studies (topography and morphology) by scanning and transmission electron microscopes (SEM/TEM) revealed different (pore, lamellar, fusion) modes of nisin release from nanoliposomes embedded in HPMC matrix. As microbiological worth, nisin nano-emulsion (encapsulated and free nisin) films were effective against potential foodborne pathogen Listeria monocytogenes. This innovative concept of biodegradable nano-active films may thus be a preventive system toward improved food safety.     

Phototransformation of the insecticide fipronil: identification of novel photoproducts and evidence for an alternative pathway of photodegradation

Fipronil is a recently discovered insecticide of the phenylpyrazole series. It has a highly selective biochemical mode of action, which has led to its use in a large number of important agronomical, household, and veterinary applications. Previous studies have shown that, during exposure to light, fipronil is converted into a desulfurated derivative (desulfinyl-fipronil), which has slightly reduced insecticidal activity. In this study, the photodegradation of fipronil was studied in solution at low light intensities (sunlight or UV lamp). In addition to desulfinyl-fipronil, a large number of minor photoproducts were observed, including diversely substituted phenylpyrazole derivatives and aniline derivatives that had lost the pyrazole ring. Desulfinylfipronil itself was shown to be relatively stable under both UV light and sunlight, with only limited changes occurring in the substitution of the aromatic ring. Since this compound accumulated to levels corresponding to only 30-55% of the amount of fipronil degraded, it was concluded that one or more alternative pathways of photodegradation must be operating. On the basis of the structurally identified photoproducts, it is proposed that fipronil photodegradation occurs via at least two distinct pathways, one of which involves desulfuration at the 4-position of the pyrazole ring giving the desulfinyl derivative and the other of which involves a different modification of the 4-substituent, leading to cleavage of the pyrazole ring and the formation of aniline derivatives. The latter compounds do not accumulate to high levels and may, therefore, be degraded further. The ecological significance of these results is discussed, particularly with regard to the insecticidal activity of the photoproducts.     

Lactobacilli as multifaceted probiotics with poorly disclosed molecular mechanisms

Lactic acid bacteria and more particularly lactobacilli have been used for the production of fermented foods for centuries. Several lactobacilli have been recognized as probiotics due to their wide range of health-promoting effects in humans. However, little is known about the molecular mechanisms underpinning their probiotic functions. Here we reviewed the main beneficial effects of lactobacilli and discussed, when the information is available, the molecular machinery involved in their probiotic function.Among the beneficial effects, lactobacilli can improve digestion, absorption and availability of nutrients. As an example, some strains are able to degrade carbohydrates such as lactose or α-galactosides that may cause abdominal pain. Furthermore, they can hydrolyze compounds that limit the bioavailability of minerals like tannin and phytate due to tannin acylhydrolase and phytase activities. In addition, it was shown that some lactobacilli strains can improve mineral absorption in Caco-2 cells. Lactobacilli can also contribute to improve the nutritional status of the host by producing B group vitamins. More recently, the role of lactobacilli in energy homeostasis, particularly in obese patients, is the object of an increased interest.Lactobacilli are also involved in the prevention of diseases. They have potential to prevent carcinogenesis through the modulation of enzymes involved in the xenobiotic pathway, and may prevent cardiovascular diseases such as hypertension through the production of a bioactive peptide that may have angiotensin converting enzyme inhibitor activity. Lactobacilli are increasingly studied for the treatment of inflammatory bowel diseases and exhibit interesting potential in the reduction of pain perception. The ability of some strains to bind to intestinal cells, their pathogen-associated molecular patterns and the metabolites they produce confer interesting immunomodulatory effects. Finally, pathogenic fungi, virus or bacteria can be inhibited by probiotics. They can reinforce the intestinal barrier, simply occupying the ecological niche, or they can have an active role by synthesizing various metabolites inhibiting pathogen development.Lactobacilli have a long standing history with foods and humans but comparatively, their history as probiotics is recent. Their effects are investigated in in vitro and in vivo models leading sometimes to contradictory or controversial results that make necessary final demonstrations through clinical trials. Researches on molecular mechanisms involved in the beneficial effects reviewed here are necessary for a better understanding of these effects, but could also lead to the development of molecular tools to help the screening of the probiotic potential of lactobacilli that are common inhabitants of numerous fermented foods around the world.     

Biosynthesis and role of 3-methylbutanal in cheese by lactic acid bacteria: Major metabolic pathways,enzymes involved,and strategies for control

Branched chain aldehyde, 3-methylbutanal is associated as a key flavor compound with many hard and semi-hard cheese varieties. The presence and impact of this flavor compound in bread, meat, and certain beverages has been recently documented, however its presence and consequences regarding cheese flavor were not clearly reported. This paper gives an overview of the role of 3-methylbutanal in cheese, along with the major metabolic pathways and key enzymes leading to its formation. Moreover, different strategies are highlighted for the control of this particular flavor compound in specific cheese types.